EP0796268B1 - Method for continuously preparing a ketose solution by isomerising aldose, and apparatus therefor - Google Patents
Method for continuously preparing a ketose solution by isomerising aldose, and apparatus therefor Download PDFInfo
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- EP0796268B1 EP0796268B1 EP95941781A EP95941781A EP0796268B1 EP 0796268 B1 EP0796268 B1 EP 0796268B1 EP 95941781 A EP95941781 A EP 95941781A EP 95941781 A EP95941781 A EP 95941781A EP 0796268 B1 EP0796268 B1 EP 0796268B1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
- C07H1/00—Processes for the preparation of sugar derivatives
- C07H1/06—Separation; Purification
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/08—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with moving particles
- B01J8/12—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with moving particles moved by gravity in a downward flow
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/16—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with particles being subjected to vibrations or pulsations
Definitions
- the invention relates to a method and a installation for the continuous preparation of a solution of ketosis - including ketohexose such as fructose - to from a starting sugar solution comprising at least an aldose - in particular an aldohexose such as glucose -.
- Sweet solutions extracted from natural materials contain osides which, by hydrolysis, produce mixed sweet solutions of ketosis, aldoses and osides.
- Aldoses including aldohexoses such as glucose, are sugars that can be obtained at a lower cost given their presence in large quantities in natural products.
- ketoses rarer in products natural, are of higher cost and are difficult to extract or obtain with great purity.
- the ketoses, and in particular ketohexoses such as fructose have interesting specific properties. In particular they have a different sweetening power and are precursors of many derivatives with properties interesting, for example the HMF. But so much for the food industry, only for the food industry organic chemistry, the use of ketosis involves have a very pure solution at low cost, in particular free of aldose whose taste properties and physicochemical are different from those of ketoses.
- the price of obtaining glucose is typically around 2 to 4 times that of sucrose (naturally occurring oside) while that of fructose is conventionally of the order of 5 to 8 times that sucrose, about 2 to 4 times that of glucose.
- the chemical isomerization of glucose into fructose in a homogeneous medium can be carried out in the presence of a basic catalysis. However, several others isomers and decomposition products are formed simultaneously (such as mannose, sorbose, psicosis, tagatose ).
- JP - 51095143 describes the isomerization of a 50 Brix glucose solution in the presence of a aluminosilicate in alkaline form in a bed column fixed.
- the fructose yield is around 40% and a subsequent separation step is required. This process also has the above-mentioned drawbacks and therefore has been exploited industrially.
- the invention therefore aims to overcome these disadvantages by proposing a method of preparation in a pure ketosis solution, including ketohexose and in particular fructose, applicable to industrial scale at a lower cost, and in particular at a cost comparable to that of aldoses, especially aldohexoses, and in particular glucose.
- the invention aims in particular to propose an economical process for continuously preparing a pure ketosis solution, from aldose solution or a mixture of aldose (s) and ketosis (s).
- the invention aims to propose a process for the preparation of a pure fructose solution from a solution of glucose, or fructose and glucose, and at a lower cost than in art previous, and in particular compatible with profitability industrial.
- the invention also aims to propose such a continuous one-step process that can be implemented industrially under conditions profitable in a facility of size and capacity reduced at low cost and operation.
- the invention further aims to provide a installation for implementing the process.
- the invention relates to a process for the continuous preparation of a ketosis solution - in particular ketohexose - from a sugar solution of departure comprising at least one aldose -in particular at least one aldohexose-, characterized in that at least one vertical continuous multicontact reactor, in that continuously introduces the starting sugar solution into the reactor, in that we circulate continuously in the reactor at least one tectosilicate or one clay capable of form a heterogeneous catalyst for isomerization of aldoses in ketosis, and in what we circulate from top to bottom at least one microporous solid in the reactor selective adsorption chosen to selectively adsorb either the aldoses of the starting solution, or the ketoses from isomerization, and be compatible with isomerization conditions.
- microporous solid generally designates any mineral compound of natural or synthetic origin formed by three-dimensional sequences of tetrahedra T0 4 with T representing at least two different elements of the periodic classification such as Si , Al, B, Fe, Ga, Ge, etc ... In this sequence, the oxygen atoms of the tetrahedra T0 4 are in common with the neighboring tetrahedra.
- a microporous solid is a solid having pores with dimensions generally less than about 10 -9 m. It should be noted that a microporous solid is distinguished from macroporous solids (whose pores have dimensions generally greater than 10 -8 m) such as resins, and mesoporous solids (whose pores have dimensions generally between 2.10 - 9 m and 10 -8 m).
- a microporous solid capable of selectively adsorb aldoses, recovering ketosis isomerized in a solvent, in particular a solvent against the current flowing from bottom to top which can be the same as that of the starting solution, namely water.
- a method according to the invention performs isomerization in a different area, -especially located below- a separation zone, including an adsorption zone for aldoses.
- the temperature within the reactor (s) according to at least two separate zones, the first of which is kept at a temperature between 30 ° C and 90 ° C chosen for promote adsorption by the microporous solid, and whose the second is maintained at a temperature between 90 ° C and 110 ° C chosen to favor the isomerization of aldoses in ketoses.
- a temperature of the order of 60 ° C. is maintained in the first adsorption zone and a temperature of the order of 95 ° C to 100 ° C in the second isomerization zone.
- the first zone adsorption is located above the introduction of the starting sugar solution in the reactor
- the second isomerization zone is located below the introduction of the starting sugar solution into the reactor.
- tectosilicates usable in within the scope of the invention, mention may be made in particular of zeolites (aluminosilicates). We can also nevertheless use borosilicates or aluminophosphates, or silicoaluminophosphates ...
- a tectosilicate functionalized with metal cations is a microporous solid which has catalytic alkali metal sites within its structure.
- a tectosilicate or a clay especially in non-form proton in particular functionalized by cations metallic - in particular alkaline or alkaline-earth-.
- the tectosilicate or clay in cationic form (not proton) is chosen to present a basicity sufficient to catalyze isomerization.
- a tectosilicate or clay as a microporous solid selective adsorption. Furthermore, according to the invention, uses a solid microporous selective adsorption in preformed pieces, especially in extruded form.
- tectosilicate or a clay which acts as catalyst in a temperature range different from one where it acts as a microporous solid adsorption selective for aldoses. More specifically, we choose a tectosilicate or clay with adsorption selective aldoses at a temperature different from that where the catalysis effect of isomerization by this solid is optimal.
- a zeolite is used as catalyst and / or selective adsorption solid.
- zeolite X in potassium form or a zeolite X in barium form.
- zeolites presenting in besides good basicity can be used alone in a method according to the invention for acting both as isomerization catalyst and selective adsorbent of aldoses as indicated above.
- zeolite X in sodium form
- zeolite Y in sodium form potassium
- zeolite X in strontium form
- zeolite Y in calcium form
- the method according to the invention is implemented in a pulsed column.
- Pulsed columns are devices known vertical multi-contact extraction or separation in which one can maintain pulsations (see for example the document "Pulsed Perforated-Plate Columns ", D.H. Logsdail, M.J. Slaten, Handbook of Solvent Extraction, Teh C. Lo Malcolm H.I. Baird, Carl Hanson, Krieiger Publishing Company, Malabar Florida, 1991, 11-2, p 335-372, incorporated by reference herein description).
- the pulsed column serves not only separator, but also and above all of continuous multicontact reactor. We thus realize simultaneously in the pulsed column, in a single step, continuous reaction and selective product extraction of reaction.
- the invention also relates to an installation implementing a method according to the invention, characterized in that it comprises a continuous reactor vertical multi-contact, in particular a pulsed column, and means of controlling the temperature prevailing within the reactor according to at least two distinct zones corresponding respectively at least two distinct temperatures.
- the installation according to the invention is also characterized in that it includes a supply of starting solution located at an intermediate level of the reactor, and in that the control means are adapted to independently control the temperature above and below the feed in the starting solution.
- the invention further relates to a method and an installation comprising all or part in combination of the characteristics mentioned above or below.
- the invention allows obtaining continuously in a single ketosis step by isomerization of aldoses.
- the installation according to the invention shown in the figure has a pulsed column 1 which acts as a continuous multicontact vertical device for reaction / extraction.
- This pulsed column 1 comprises a power supply 2 at the bottom 3 by which one can introduce a liquid, in particular water, and an outlet 4 at its top 5 by which the ketosis solution pure prepared is extracted.
- the pulsed column 1 has a feed 6 in starting sugar solution, located at an intermediate level, i.e. between feeding 2 lower in water and the upper 4 extraction of the ketosis solution.
- Supply 6 in starting solution is located at least at a substantially median level in the example shown. According to the respective kinetics of adsorption and isomerization, feed 2 can be moved up or down relative to the example shown schematically in the figure.
- Pulsed column 1 also has of a superior introduction 7 of solid compound (s) in pieces 8. These pieces 8 of solid compound (s) flow from top to bottom and are therefore recovered at the party lower 3 of the pulsed column 1 by an outlet 9.
- an X zeolite is used in potassium form or in preformed barium form (extruded into balls, sticks, cylinders, ...), this zeolite simultaneously acts as a catalyst isomerization and microporous adsorption solid selective for aldoses, including glucose.
- Such a zeolite indeed forms an adsorbent molecular sieve preferentially glucose compared to fructose. These pieces therefore flow from top to bottom through the column pulsed 1, and against the current of the liquid phase which flows from bottom to top.
- an isomerization catalyst separate from the compound solid selective adsorption.
- This catalyst can be introduced simultaneously with the pieces of solid compound adsorption at the top 5 of column 1, or on the contrary be mixed in powder form in suspension in the starting sugar solution, thanks to a mixer located upstream of supply 6 which is then moved to the lower part 3 of the pulsed column 1.
- a filter is provided at the outlet of extraction 4 of the ketosis solution to separate the catalyst suspended in this solution.
- the catalyst must not act of selective adsorption compound of either sugars.
- the 8 pieces of solid compound (s) collected at the bottom 3 of the pulsed column 1 are brought to a filter 10, thanks to a device hydraulic lift.
- the 8 pieces can be recovered by processing carried out by consisting of desorbing the aldoses and refunctionalize the solid compound to make it new able to perform the functions for which it is means.
- a zeolite X under potassium form it can be calcined to desorb the aldoses, then refunctionalized in potassium form.
- the pieces 8 of compound (s) solid (s) can be recycled to the top 5 of the pulsed column 1.
- the installation includes means 12, 13 for controlling the temperature prevailing within of the pulsed column 1 in at least two zones 14, 15 distinct corresponding respectively to at least two separate temperatures.
- These means 12, 13 for controlling temperatures are able to independently control the temperature above (in the upper zone 14) and at below (in the lower zone 15) of the power supply 6 in starting solution.
- the column Pulsed 1 has two double envelopes 12, 13, to know a double upper envelope 12 arranged above of the feed 6 in starting solution, and a double jacket 13 arranged below the feed 6 starting solution.
- a feeding and checking the operation of the double envelopes 12, 13 is provided in a manner known per se and not shown in the figure.
- the upper zone 14 of the reactor located opposite of the upper double jacket 12 can thus be maintained at a temperature different from zone 15 lower opposite the lower double envelope 13. And we can independently control each other. temperatures prevailing in each of these zones 14, 15.
- the area upper 14 constitutes a first adsorption zone in which maintains a temperature between 30 ° C. and 90 ° C, in particular of the order of 60 ° C, chosen for promote adsorption by the microporous solid, in particular selective adsorption of aldoses by zeolite X under potassium or barium form.
- the lower zone 15 constitutes a second isomerization zone in which maintains a temperature between 90 ° C and 110 ° C, in particular of the order of 95 ° C., to favor the isomerization of aldoses to ketoses in the presence of isomerization catalyst.
- the 8 pieces of absorbent zeolite selectively capture aldoses, in particular glucose, in solution in the phase liquid and transport them to the lower zone 15 isomerization.
- the aldoses adsorbed on the zeolite are isomerized by the sites cationic, and the water current captures the ketoses formed, especially the fructose that is entrained, with the fructose possibly from food 6 of the solution of departure, up to exit 4 upper.
- the pulsed column 1 has a device 16 able to maintain pulsations of the phases liquids, in a manner known per se.
- the amplitude and frequency of the pulsations are determined to ensure proper traffic above-described liquid and solid phases. So does even the lining of the pulsed column which can be type baskets and crowns or discs and crowns.
- the zeolite used has a partition coefficient of fructose adsorption relative with glucose as it is highly selective with respect to glucose.
- the starting glucose solution had a concentration of 500 g per liter.
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Abstract
Description
L'invention concerne un procédé et une installation de préparation en continu d'une solution de cétose -notamment de cétohexose tel que le fructose- à partir d'une solution sucrée de départ comprenant au moins un aldose -notamment un aldohexose tel que le glucose-.The invention relates to a method and a installation for the continuous preparation of a solution of ketosis - including ketohexose such as fructose - to from a starting sugar solution comprising at least an aldose - in particular an aldohexose such as glucose -.
Les solutions sucrées extraites des matières naturelles (chicorée, betterave, canne à sucre, blé...) contiennent des osides qui, par hydrolyse, produisent des solutions sucrées mixtes de cétoses, d'aldoses et d'osides. Les aldoses, et notamment les aldohexoses tels que le glucose, sont des sucres qui peuvent être obtenus à moindre coût compte tenu de leur présence en grande quantité dans les produits naturels. Au contraire, les cétoses, plus rares dans les produits naturels, sont de coût plus élevé et sont difficiles à extraire ou à obtenir avec une grande pureté. Or, les cétoses, et notamment les cétohexoses tels que le fructose, possèdent des propriétés spécifiques intéressantes. En particulier, ils ont un pouvoir édulcorant différent et sont des précurseurs de nombreux dérivés aux propriétés intéressantes, par exemple le HMF. Mais tant pour l'industrie agro-alimentaire, que pour l'industrie de la chimie organique, l'utilisation des cétoses suppose de disposer à moindre coût d'une solution d'une grande pureté, notamment exempte d'aldose dont les propriétés gustatives et physico-chimiques sont différentes de celles des cétoses.Sweet solutions extracted from natural materials (chicory, beet, sugar cane, wheat ...) contain osides which, by hydrolysis, produce mixed sweet solutions of ketosis, aldoses and osides. Aldoses, including aldohexoses such as glucose, are sugars that can be obtained at a lower cost given their presence in large quantities in natural products. At on the contrary, ketoses, rarer in products natural, are of higher cost and are difficult to extract or obtain with great purity. However, the ketoses, and in particular ketohexoses such as fructose, have interesting specific properties. In particular they have a different sweetening power and are precursors of many derivatives with properties interesting, for example the HMF. But so much for the food industry, only for the food industry organic chemistry, the use of ketosis involves have a very pure solution at low cost, in particular free of aldose whose taste properties and physicochemical are different from those of ketoses.
Par exemple, le prix d'obtention du glucose est classiquement de l'ordre de 2 à 4 fois celui du saccharose (oside d'origine naturelle) alors que celui du fructose est classiquement de l'ordre de 5 à 8 fois celui du saccharose, soit de l'ordre de 2 à 4 fois celui du glucose.For example, the price of obtaining glucose is typically around 2 to 4 times that of sucrose (naturally occurring oside) while that of fructose is conventionally of the order of 5 to 8 times that sucrose, about 2 to 4 times that of glucose.
On a déjà pensé à isomérer les aldoses en cétoses et notamment le glucose en fructose. Cette réaction d'isomérisation est un équilibre difficile à déplacer et qui ne permet pas d'obtenir une pureté de 100 % de cétose par voie chimique. Il est donc nécessaire d'avoir recours à une étape d'extraction ultérieure qui, elle-même, n'aboutit pas à une pureté parfaite de 100 % en cétose à un coût raisonnable (cf US-A-4.373.025).We have already thought about isomerizing the aldoses in ketoses and especially glucose to fructose. This reaction isomerization is a difficult balance to move and which does not allow to obtain a purity of 100% of ketosis chemically. It is therefore necessary to have recourse to a subsequent extraction step which itself does not succeed not at 100% perfect purity in ketosis at a cost reasonable (see US-A-4,373,025).
L'isomérisation chimique du glucose en fructose en milieu homogène peut être effectuée en présence d'une catalyse basique. Néanmoins, plusieurs autres isomères ainsi que des produits de décomposition se forment simultanément (tels que le mannose, le sorbose, le psicose, le tagatose...).The chemical isomerization of glucose into fructose in a homogeneous medium can be carried out in the presence of a basic catalysis. However, several others isomers and decomposition products are formed simultaneously (such as mannose, sorbose, psicosis, tagatose ...).
L'isomérisation du glucose en fructose en présence d'une résine échangeuse d'ions a aussi été envisagée. Néanmoins, le fructose formé diffuse dans la résine et se dégrade plus rapidement que le glucose. Dès lors, les procédés connus conduisent à des purifications difficiles dues à la présence de produits colorés, d'odeurs, de cendres...The isomerization of glucose into fructose into presence of an ion exchange resin has also been considered. Nevertheless, the fructose formed diffuses in the resin and degrades faster than glucose. From therefore, known methods lead to purifications difficult due to the presence of colored products, smells, ashes ...
On a aussi envisagé d'effectuer l'isomérisation en présence d'une enzyme. Néanmoins, les inconvénients de ce type de réaction résident dans le prix de production de l'enzyme et dans la sensibilité aux paramètres extérieurs (Ph, température...). En outre, l'isomérisation enzymatique conduit (à partir de glucose pur) à des taux de fructose nécessitant une séparation ultérieure.We also considered carrying out isomerization in the presence of an enzyme. Nevertheless, the disadvantages of this type of reaction lie in the price of enzyme production and in sensitivity to external parameters (Ph, temperature ...). In addition, enzymatic isomerization leads (from glucose pure) at fructose levels requiring separation later.
JP - 51095143 décrit l'isomérisation d'une solution de glucose à 50 Brix en présence d'un aluminosilicate sous forme alcaline dans une colonne à lit fixe. Le rendement en fructose est de l'ordre de 40% et une étape ultérieure de séparation est nécessaire. Ce procédé présente aussi les inconvénients sus-mentionnés et n'a donc pa été exploité industriellement.JP - 51095143 describes the isomerization of a 50 Brix glucose solution in the presence of a aluminosilicate in alkaline form in a bed column fixed. The fructose yield is around 40% and a subsequent separation step is required. This process also has the above-mentioned drawbacks and therefore has been exploited industrially.
L'invention vise donc à pallier ces inconvénients en proposant un procédé de préparation en continu d'une solution pure de cétose, notamment de cétohexose et en particulier de fructose, applicable à l'échelle industrielle à moindre coût, et notamment à un coût comparable à celui des aldoses, notamment des aldohexoses, et en particulier du glucose.The invention therefore aims to overcome these disadvantages by proposing a method of preparation in a pure ketosis solution, including ketohexose and in particular fructose, applicable to industrial scale at a lower cost, and in particular at a cost comparable to that of aldoses, especially aldohexoses, and in particular glucose.
L'invention vise en particulier à proposer un procédé économique de préparation en continu d'une solution pure de cétose, à partir d'une solution d'aldose ou d'un mélange d'aldose(s) et de cétose(s).The invention aims in particular to propose an economical process for continuously preparing a pure ketosis solution, from aldose solution or a mixture of aldose (s) and ketosis (s).
En particulier, l'invention vise à proposer un procédé de préparation d'une solution pure de fructose à partir d'une solution de glucose, ou de fructose et de glucose, et ce à un coût plus faible que dans l'art antérieur, et notamment compatible avec une rentabilité industrielle.In particular, the invention aims to propose a process for the preparation of a pure fructose solution from a solution of glucose, or fructose and glucose, and at a lower cost than in art previous, and in particular compatible with profitability industrial.
L'invention vise aussi à proposer un tel procédé effectué en continu en une seule étape et qui peut être mis en oeuvre industriellement dans des conditions rentables dans une installation de taille et de capacité réduites à faibles prix de revient et coûts de fonctionnement.The invention also aims to propose such a continuous one-step process that can be implemented industrially under conditions profitable in a facility of size and capacity reduced at low cost and operation.
L'invention vise en outre à proposer une installation de mise en oeuvre du procédé.The invention further aims to provide a installation for implementing the process.
Pour ce faire, l'invention concerne un procédé de préparation en continu d'une solution de cétose -notamment de cétohexose- à partir d'une solution sucrée de départ comprenant au moins un aldose -notamment au moins un aldohexose-, caractérisé en ce qu'on utilise au moins un réacteur multicontact continu vertical, en ce qu'on introduit en continu la solution sucrée de départ dans le réacteur, en ce qu'on fait circuler en continu dans le réacteur au moins un tectosilicate ou une argile apte à former un catalyseur hétérogène d'isomérisation des aldoses en cétoses, et en ce qu'on fait circuler de haut en bas dans le réacteur au moins un solide microporeux d'adsorption sélective choisi pour adsorber sélectivement soit les aldoses de la solution de départ, soit les cétoses issus de l'isomérisation, et être compatible avec les conditions d'isomérisation. To do this, the invention relates to a process for the continuous preparation of a ketosis solution - in particular ketohexose - from a sugar solution of departure comprising at least one aldose -in particular at least one aldohexose-, characterized in that at least one vertical continuous multicontact reactor, in that continuously introduces the starting sugar solution into the reactor, in that we circulate continuously in the reactor at least one tectosilicate or one clay capable of form a heterogeneous catalyst for isomerization of aldoses in ketosis, and in what we circulate from top to bottom at least one microporous solid in the reactor selective adsorption chosen to selectively adsorb either the aldoses of the starting solution, or the ketoses from isomerization, and be compatible with isomerization conditions.
Dans toute la présente demande, l'expression "solide microporeux" désigne de façon générale tout composé minéral d'origine naturelle ou synthétique formé par des enchaínements tridimensionnels de tétraèdres T04 avec T représentant au moins deux éléments différents de la classification périodique tels que Si, Al, B, Fe, Ga, Ge, etc... Dans cet enchaínement, les atomes d'oxygène des tétraèdres T04 sont en commun avec les tétraèdres voisins.Throughout the present application, the expression “microporous solid” generally designates any mineral compound of natural or synthetic origin formed by three-dimensional sequences of tetrahedra T0 4 with T representing at least two different elements of the periodic classification such as Si , Al, B, Fe, Ga, Ge, etc ... In this sequence, the oxygen atoms of the tetrahedra T0 4 are in common with the neighboring tetrahedra.
Un solide microporeux est un solide présentant des pores de dimensions généralement inférieures à environ 10-9 m. Il est à noter qu'un solide microporeux se distingue des solides macroporeux (dont les pores ont des dimensions généralement supérieures à 10-8 m) tels que les résines, et des solides mésoporeux (dont les pores ont des dimensions généralement comprises entre 2.10-9 m et 10-8 m).A microporous solid is a solid having pores with dimensions generally less than about 10 -9 m. It should be noted that a microporous solid is distinguished from macroporous solids (whose pores have dimensions generally greater than 10 -8 m) such as resins, and mesoporous solids (whose pores have dimensions generally between 2.10 - 9 m and 10 -8 m).
Si on utilise un solide d'adsorption sélective des cétoses, une étape de désorption ultérieure est prévue. Une telle étape est néanmoins simple, peu coûteuse et fournit les cétoses avec une grande pureté.If we use an adsorption solid selective ketosis, a subsequent desorption step is planned. Such a step is nevertheless simple, little expensive and provides ketosis with high purity.
Si on utilise un solide microporeux apte à adsorber sélectivement les aldoses, on récupère le cétose isomérisé dans un solvant, notamment un solvant à contre-courant circulant de bas en haut qui peut être le même que celui de la solution de départ, à savoir de l'eau.If we use a microporous solid capable of selectively adsorb aldoses, recovering ketosis isomerized in a solvent, in particular a solvent against the current flowing from bottom to top which can be the same as that of the starting solution, namely water.
L'invention concerne donc aussi un procédé caractérisé en ce que :
- on utilise un seul réacteur multicontact,
- on introduit la solution sucrée de départ à un niveau intermédiaire du réacteur,
- on choisit au moins un solide microporeux d'adsorption sélective des aldoses de la solution sucrée de départ,
- on introduit dans le réacteur un courant continu d'un solvant de la solution sucrée de départ à un niveau du réacteur inférieur à celui auquel on introduit la solution sucrée de départ,
- on extrait en continu, à contre-courant, la solution de cétose à un niveau du réacteur au-dessus de celui auquel on introduit la solution sucrée de départ, de sorte que le procédé peut être effectué en continu en une seule étape dans un seul réacteur.
- we use a single multicontact reactor,
- the starting sugar solution is introduced at an intermediate level of the reactor,
- at least one microporous solid for selective adsorption of the aldoses of the starting sugar solution is chosen,
- a continuous stream of a solvent for the starting sugar solution is introduced into the reactor at a level of the reactor lower than that to which the starting sugar solution is introduced,
- the ketose solution is continuously extracted against the current at a level of the reactor above that to which the starting sugar solution is introduced, so that the process can be carried out continuously in a single step in a single reactor.
Dans un procédé selon l'invention, on effectue l'isomérisation dans une zone différente, -notamment située en dessous- d'une zone de séparation, notamment d'une zone d'adsorption des aldoses.In a method according to the invention, performs isomerization in a different area, -especially located below- a separation zone, including an adsorption zone for aldoses.
Selon l'invention, on contrôle la température au sein du(des) réacteur(s) selon au moins deux zones distinctes dont la première est maintenue à une température comprise entre 30° C et 90° C choisie pour favoriser l'adsorption par le solide microporeux, et dont la deuxième est maintenue à une température comprise entre 90° C et 110° C choisie pour favoriser l'isomérisation des aldoses en cétoses. Avantageusement et selon l'invention, on maintient une température de l'ordre de 60° C dans la première zone d'adsorption et une température de l'ordre de 95° C à 100° C dans la deuxième zone d'isomérisation.According to the invention, the temperature within the reactor (s) according to at least two separate zones, the first of which is kept at a temperature between 30 ° C and 90 ° C chosen for promote adsorption by the microporous solid, and whose the second is maintained at a temperature between 90 ° C and 110 ° C chosen to favor the isomerization of aldoses in ketoses. Advantageously and according to the invention, a temperature of the order of 60 ° C. is maintained in the first adsorption zone and a temperature of the order of 95 ° C to 100 ° C in the second isomerization zone.
Selon l'invention, la première zone d'adsorption est située au-dessus de l'introduction de la solution sucrée de départ dans le réacteur, et la deuxième zone d'isomérisation est située en-dessous de l'introduction de la solution sucrée de départ dans le réacteur. Ainsi, on maintient des températures différentes au-dessus et en dessous de l'introduction de la solution de départ dans le réacteur, à savoir une température comprise entre 30° C et 90° C, notamment de l'ordre de 60° C correspondant à la première zone d'adsorption des aldoses par le solide microporeux au-dessus de l'introduction de la solution de départ, et une température comprise entre 90° C et 110° C, notamment de l'ordre de 95° C, correspondant à une deuxième zone d'isomérisation en dessous de l'introduction de la solution de départ.According to the invention, the first zone adsorption is located above the introduction of the starting sugar solution in the reactor, and the second isomerization zone is located below the introduction of the starting sugar solution into the reactor. So we maintain different temperatures above and below the introduction of the solution of leaving in the reactor, namely a temperature comprised between 30 ° C and 90 ° C, especially around 60 ° C corresponding to the first adsorption zone for aldoses by the microporous solid above the introduction of the starting solution, and a temperature between 90 ° C and 110 ° C, in particular of the order of 95 ° C, corresponding to a second isomerization zone below the introduction of the starting solution.
L'introduction d'un solvant (eau) en partie inférieure permet de laver le solide microporeux et de capter les cétoses formés par isomérisation.The introduction of a solvent (water) in part lower makes it possible to wash the microporous solid and capture the ketoses formed by isomerization.
Les tectosilicates sont des composés microporeux caractérisés par une structure comportant :
- une charpente tridimensionnelle formée par l'enchaínement de tétraèdres TO4, SiO4, T représentant un élément de la classification tel que Al, B, Ga, Ge,... et,
- un réseau monodimensionnel, bidimensionnel, ou tridimensionnel de canaux et cavités de dimensions moléculaires contenant des cations de compensation éventuels, de l'eau ou d'autres molécules ou sels.
- a three-dimensional framework formed by the sequence of tetrahedrons TO4, SiO4, T representing an element of the classification such as Al, B, Ga, Ge, ... and,
- a one-dimensional, two-dimensional, or three-dimensional network of molecular-size channels and cavities containing possible compensation cations, water or other molecules or salts.
Parmi les tectosilicates utilisables dans le cadre de l'invention, on peut citer notamment les zéolithes (aluminosilicates). On peut aussi néanmoins utiliser des borosilicates ou des aluminophosphates, ou des silicoaluminophosphates...Among the tectosilicates usable in within the scope of the invention, mention may be made in particular of zeolites (aluminosilicates). We can also nevertheless use borosilicates or aluminophosphates, or silicoaluminophosphates ...
Un tectosilicate fonctionnalisé par des cations métalliques est un solide microporeux qui présente des sites métalliques alcalins catalytiques au sein de sa structure.A tectosilicate functionalized with metal cations is a microporous solid which has catalytic alkali metal sites within its structure.
Egalement, selon l'invention, on utilise, à titre de catalyseur hétérogène d'isomérisation, un tectosilicate ou une argile, notamment sous forme non protonique en particulier fonctionnalisé par des cations métalliques -notamment alcalins ou alcalino-terreux-. Le tectosilicate ou argile sous forme cationique (non protonique) est choisi pour présenter une basicité suffisante pour catalyser l'isomérisation.Also, according to the invention, as a heterogeneous isomerization catalyst, a tectosilicate or a clay, especially in non-form proton in particular functionalized by cations metallic - in particular alkaline or alkaline-earth-. The tectosilicate or clay in cationic form (not proton) is chosen to present a basicity sufficient to catalyze isomerization.
Egalement, selon l'invention, on utilise un tectosilicate ou une argile à titre de solide microporeux d'adsorption sélective. En outre, selon l'invention, on utilise un solide microporeux d'adsorption sélective en morceaux préformés, notamment sous forme extrudée.Also, according to the invention, a tectosilicate or clay as a microporous solid selective adsorption. Furthermore, according to the invention, uses a solid microporous selective adsorption in preformed pieces, especially in extruded form.
Dans une première variante de l'invention, on choisit et on utilise un catalyseur distinct du solide microporeux d'adsorption sélective.In a first variant of the invention, we choose and use a catalyst separate from the solid microporous selective adsorption.
Dans une deuxième variante de l'invention, on choisit et on utilise un tectosilicate ou une argile apte à faire office simultanément de catalyseur d'isomérisation et de solide microporeux d'adsorption sélective. In a second variant of the invention, we choose and use a tectosilicate or a clay able to act simultaneously as a catalyst isomerization and microporous adsorption solid selective.
Dans ce cas, selon l'invention, on choisit un tectosilicate ou une argile qui fait office de catalyseur dans une plage de températures différente de celle où il fait office de solide microporeux d'adsorption sélective des aldoses. Plus particulièrement, on choisit un tectosilicate ou une argile présentant une adsorption sélective des aldoses à une température distincte de celle où l'effet de catalyse de l'isomérisation par ce solide est optimale.In this case, according to the invention, we choose a tectosilicate or a clay which acts as catalyst in a temperature range different from one where it acts as a microporous solid adsorption selective for aldoses. More specifically, we choose a tectosilicate or clay with adsorption selective aldoses at a temperature different from that where the catalysis effect of isomerization by this solid is optimal.
On sait définir les caractéristiques d'un solide microporeux pour qu'il présente une adsorption sélective à l'égard soit des aldoses (notamment du glucose), soit des cétoses (notamment du fructose). Selon l'invention, on utilise une zéolithe à titre de catalyseur et/ou de solide d'adsorption sélective.We know how to define the characteristics of a microporous solid so that it has adsorption selective for either aldoses (especially glucose), or ketoses (especially fructose). According to the invention, a zeolite is used as catalyst and / or selective adsorption solid.
Selon l'invention, à titre de solide d'adsorption sélective des aldoses, notamment du glucose, on utilise une zéolithe X sous forme potassium ou une zéolithe X sous forme baryum. Ces zéolithes présentant en outre une bonne basicité peuvent être utilisées seules dans un procédé selon l'invention pour faire office à la fois de catalyseur d'isomérisation et d'adsorbant sélectif des aldoses comme indiqué ci-dessus.According to the invention, as a solid selective adsorption of aldoses, especially glucose, we use a zeolite X in potassium form or a zeolite X in barium form. These zeolites presenting in besides good basicity can be used alone in a method according to the invention for acting both as isomerization catalyst and selective adsorbent of aldoses as indicated above.
A titre de solide d'adsorption sélective des cétoses, notamment du fructose, on peut utiliser une zéolithe X sous forme sodium, ou une zéolithe Y sous forme potassium, ou une zéolithe X sous forme strontium ou une zéolithe Y sous forme calcium.As a selective adsorption solid ketoses, especially fructose, one can use a zeolite X in sodium form, or a zeolite Y in sodium form potassium, or a zeolite X in strontium form or a zeolite Y in calcium form.
Avantageusement, le procédé selon l'invention est mis en oeuvre dans une colonne pulsée.Advantageously, the method according to the invention is implemented in a pulsed column.
Les colonnes pulsées sont des dispositifs connus multicontacts verticaux d'extraction ou de séparation dans lesquels on peut entretenir des pulsations (cf par exemple le document "Pulsed Perforated-Plate Columns", D.H. Logsdail, M.J. Slaten, Handbook of Solvent Extraction, Teh C.Lo Malcolm H.I. Baird, Carl Hanson, Krieiger Publishing Company, Malabar Florida, 1991, 11-2, p 335-372, incorporé par référence à la présente description).Pulsed columns are devices known vertical multi-contact extraction or separation in which one can maintain pulsations (see for example the document "Pulsed Perforated-Plate Columns ", D.H. Logsdail, M.J. Slaten, Handbook of Solvent Extraction, Teh C. Lo Malcolm H.I. Baird, Carl Hanson, Krieiger Publishing Company, Malabar Florida, 1991, 11-2, p 335-372, incorporated by reference herein description).
Il est à noter que dans un procédé selon l'invention, la colonne pulsée fait office non pas uniquement de séparateur, mais également et surtout de réacteur multicontact continu. On réalise ainsi simultanément dans la colonne pulsée, en une seule étape, la réaction et l'extraction sélective en continu du produit de réaction.It should be noted that in a process according to the invention, the pulsed column serves not only separator, but also and above all of continuous multicontact reactor. We thus realize simultaneously in the pulsed column, in a single step, continuous reaction and selective product extraction of reaction.
L'invention concerne aussi une installation de mise en oeuvre d'un procédé selon l'invention, caractérisée en ce qu'elle comporte un réacteur continu vertical multicontact, notamment une colonne pulsée, et des moyens de contrôle de la température régnant au sein du réacteur selon au moins deux zones distinctes correspondant respectivement à au moins deux températures distinctes.The invention also relates to an installation implementing a method according to the invention, characterized in that it comprises a continuous reactor vertical multi-contact, in particular a pulsed column, and means of controlling the temperature prevailing within the reactor according to at least two distinct zones corresponding respectively at least two distinct temperatures.
L'installation selon l'invention est aussi caractérisée en ce qu'elle comporte une alimentation en solution de départ située à un niveau intermédiaire du réacteur, et en ce que les moyens de contrôle sont adaptés pour contrôler indépendamment la température au-dessus et en dessous de l'alimentation en solution de départ.The installation according to the invention is also characterized in that it includes a supply of starting solution located at an intermediate level of the reactor, and in that the control means are adapted to independently control the temperature above and below the feed in the starting solution.
L'invention concerne en outre un procédé et une installation comprenant en combinaison tout ou partie des caractéristiques mentionnées ci-dessus ou ci-après.The invention further relates to a method and an installation comprising all or part in combination of the characteristics mentioned above or below.
L'invention permet l'obtention en continu en une seule étape de cétoses par isomérisation d'aldoses.The invention allows obtaining continuously in a single ketosis step by isomerization of aldoses.
Il est à noter à cet égard que les caractéristiques combinées de l'invention permettent l'obtention de ce résultat par le fait qu'il est possible d'opérer avec des sirops concentrés (Brix supérieur à 65) à haute température, avec une faible durée de réaction, les conditions réactionnelles (notamment l'absorption simultanée) déplaçant l'équilibre fortement.It should be noted in this regard that the combined features of the invention allow obtaining this result by the fact that it is possible to operate with concentrated syrups (Brix greater than 65) at high temperature, with a short reaction time, the reaction conditions (including absorption simultaneous) shifting the balance strongly.
D'autres caractéristiques et avantages de l'invention apparaítront à la lumière de la description suivante qui se réfère à la figure unique annexée qui est un schéma d'une installation de mise en oeuvre d'un procédé selon l'invention de préparation en continu en une seule étape d'une solution pure de cétose.Other features and benefits of the invention will appear in the light of the description following which refers to the single appended figure which is a diagram of an installation for implementing a process according to the invention of continuous preparation in one step of a pure ketosis solution.
L'installation selon l'invention
représentée sur la figure comporte une colonne pulsée 1 qui
fait office de dispositif vertical multicontact continu de
réaction/extraction. Cette colonne pulsée 1 comprend une
alimentation 2 en partie inférieure 3 par laquelle on peut
introduire un liquide, notamment de l'eau, et une sortie 4
à sa partie supérieure 5 par laquelle la solution de cétose
pure préparée est extraite.The installation according to the invention
shown in the figure has a
En outre, la colonne pulsée 1 est dotée
d'une alimentation 6 en solution sucrée de départ, située à
un niveau intermédiaire, c'est-à-dire entre l'alimentation
2 inférieure en eau et l'extraction 4 supérieure de la
solution de cétose. L'alimentation 6 en solution de départ
est située à un niveau au moins sensiblement médian dans
l'exemple représenté. Selon les cinétiques respectives de
l'adsorption et de l'isomérisation, l'alimentation 2 peut
être déplacée vers le haut ou vers le bas par rapport à
l'exemple représenté schématiquement sur la figure.In addition, the
La colonne pulsée 1 est également dotée
d'une introduction 7 supérieure de composé(s) solide(s) en
morceaux 8. Ces morceaux 8 de composé(s) solide(s)
circulent de haut en bas et sont donc récupérés à la partie
inférieure 3 de la colonne pulsée 1 par une sortie 9.
Dans le cas où on utilise une zéolithe X sous forme potassium ou sous forme baryum préformée (extrudée en billes, bâtonnets, cylindres, ...), cette zéolithe fait office simultanément de catalyseur d'isomérisation et de solide microporeux d'adsorption sélective des aldoses, et notamment du glucose. Une telle zéolithe forme en effet un tamis moléculaire adsorbant préférentiellement le glucose par rapport au fructose. Ces morceaux circulent donc de haut en bas à travers la colonne pulsée 1, et à contre-courant de la phase liquide qui circule de bas en haut.In the case where an X zeolite is used in potassium form or in preformed barium form (extruded into balls, sticks, cylinders, ...), this zeolite simultaneously acts as a catalyst isomerization and microporous adsorption solid selective for aldoses, including glucose. Such a zeolite indeed forms an adsorbent molecular sieve preferentially glucose compared to fructose. These pieces therefore flow from top to bottom through the column pulsed 1, and against the current of the liquid phase which flows from bottom to top.
En variante non représentée, on pourrait
utiliser un catalyseur d'isomérisation distinct du composé
solide d'adsorption sélective. Ce catalyseur peut être
introduit en simultané avec les morceaux de composé solide
d'adsorption à la partie supérieure 5 de la colonne 1, ou
au contraire être mélangé sous forme pulvérulente en
suspension dans la solution sucrée de départ, grâce à un
mélangeur situé en amont de l'alimentation 6 qui est alors
déplacée en partie inférieure 3 de la colonne pulsée 1.
Dans ce dernier cas, un filtre est prévu à la sortie de
l'extraction 4 de la solution de cétose pour séparer le
catalyseur en suspension dans cette solution. Egalement,
dans cette variante, le catalyseur ne doit pas faire office
de composé d'adsorption sélective de l'un ou l'autre des
sucres.In a variant not shown, one could
use an isomerization catalyst separate from the compound
solid selective adsorption. This catalyst can be
introduced simultaneously with the pieces of solid compound
adsorption at the
Les morceaux 8 de composé(s) solide(s)
récupérés à la partie inférieure 3 de la colonne pulsée 1
sont amenés à un filtre 10, grâce à un dispositif
d'ascenseur hydraulique. A la sortie du filtre 10, les
morceaux 8 peuvent être récupérés par un traitement
effectué en 11 consistant à désorber les aldoses et à
refonctionnaliser le composé solide pour le rendre à
nouveau apte à remplir les fonctions auxquelles on le
désigne. Par exemple, dans le cas d'une zéolithe X sous
forme potassium, celle-ci peut être calcinée pour désorber
les aldoses, puis refonctionnalisée sous forme potassium. A
la sortie du traitement 11, les morceaux 8 de composé(s)
solide(s) peuvent être recyclés à la partie supérieure 5 de
la colonne pulsée 1.8 pieces of solid compound (s)
collected at the
En outre, l'installation comporte des
moyens 12, 13 de contrôle de la température régnant au sein
de la colonne pulsée 1 selon au moins deux zones 14, 15
distinctes correspondant respectivement à au moins deux
températures distinctes. Ces moyens 12, 13 de contrôle de
températures sont aptes à contrôler indépendamment la
température au-dessus (dans la zone supérieure 14) et en
dessous (dans la zone inférieure 15) de l'alimentation 6 en
solution de départ.In addition, the installation includes
Dans l'exemple représenté, la colonne
pulsée 1 est dotée de deux doubles enveloppes 12, 13, à
savoir une double enveloppe supérieure 12 disposée au-dessus
de l'alimentation 6 en solution de départ, et une
double enveloppe 13 disposée en dessous de l'alimentation 6
de solution de départ. Un dispositif d'alimentation et de
contrôle du fonctionnement des doubles enveloppes 12, 13
est prévu de façon connue en soi et non représentée sur la
figure. La zone 14 supérieure du réacteur située en regard
de la double enveloppe supérieure 12 peut ainsi être
maintenue à une température différente de la zone 15
inférieure en regard de la double enveloppe inférieure 13.
Et on peut contrôler indépendamment l'une de l'autre les.
températures régnant respectivement dans chacune de ces
zones 14, 15.In the example shown, the
Dans le procédé selon l'invention, la zone
supérieure 14 constitue une première zone d'adsorption dans
laquelle on maintient une température comprise entre 30° C
et 90° C, notamment de l'ordre de 60° C, choisie pour
favoriser l'adsorption par le solide microporeux, notamment
l'adsorption sélective des aldoses par la zéolithe X sous
forme potassium ou baryum. La zone inférieure 15 constitue
une deuxième zone d'isomérisation dans laquelle on
maintient une température comprise entre 90° C et 110° C,
notamment de l'ordre de 95° C, pour favoriser
l'isomérisation des aldoses en cétoses en présence du
catalyseur d'isomérisation.In the method according to the invention, the area
upper 14 constitutes a first adsorption zone in
which maintains a temperature between 30 ° C.
and 90 ° C, in particular of the order of 60 ° C, chosen for
promote adsorption by the microporous solid, in particular
selective adsorption of aldoses by zeolite X under
potassium or barium form. The
Ainsi, dans la zone supérieure 14, les
morceaux 8 de zéolithe absorbante captent sélectivement les
aldoses, notamment le glucose, en solution dans la phase
liquide et les transportent jusqu'à la zone inférieure 15
d'isomérisation. Dans cette zone inférieure, les aldoses
adsorbés sur la zéolithe sont isomérisés par les sites
cationiques, et le courant d'eau capte les cétoses formés,
notamment le fructose qui est entraíné, avec le fructose
issu éventuellement de l'alimentation 6 de la solution de
départ, jusqu'à la sortie 4 supérieure.Thus, in the
Enfin, la colonne pulsée 1 est dotée d'un
dispositif 16 apte à entretenir des pulsations des phases
liquides, de façon connue en soi. Finally, the
L'amplitude et la fréquence des pulsations sont déterminées pour assurer les circulations appropriées sus-décrites des phases liquides et solides. Il en va de même du garnissage de la colonne pulsée qui peut être du type paniers et couronnes ou disques et couronnes.The amplitude and frequency of the pulsations are determined to ensure proper traffic above-described liquid and solid phases. So does even the lining of the pulsed column which can be type baskets and crowns or discs and crowns.
On étudie la réaction d'isomérisation d'une solution de départ de glucose en fructose avec une zéolithe X sous forme potassium.We study the isomerization reaction of a glucose to fructose starting solution with a zeolite X in potassium form.
Dans un réacteur de 500 ml discontinu agité, on réalise un sirop de glucose en introduisant 170 g de glucose avec de l'eau. On chauffe le réacteur à 95° C tout en agitant la solution jusqu'à la dissolution complète du glucose.In a 500 ml batch reactor stirred, we make a glucose syrup by introducing 170 g glucose with water. The reactor is heated to 95 ° C while stirring the solution until complete dissolution glucose.
On ajoute ensuite 102 g de zéolithe X sous forme potassium préalablement imprégnée du restant d'eau à 95° C.102 g of zeolite X are then added under potassium form previously impregnated with the remaining water to 95 ° C.
La zéolithe utilisée présente une coefficient de partage d'adsorption du fructose par rapport au glucose tel qu'elle est fortement sélective vis-à-vis du glucose. On peut par exemple utiliser la zéolithe X sous forme potassium telle que décrite dans la publication "A liquide phase chromatographic study of sorption and diffusion of glucose and fructose in NAX and KX zeolite crystals", Ching et al., Zeolites, 1988, vol. 8, pages 68 à 73.The zeolite used has a partition coefficient of fructose adsorption relative with glucose as it is highly selective with respect to glucose. We can for example use the zeolite X under potassium form as described in the publication "A liquid phase chromatographic study of sorption and diffusion of glucose and fructose in NAX and KX zeolite crystals ", Ching et al., Zeolites, 1988, vol. 8, pages 68 to 73.
Après une durée de réaction de 45 min, correspondant à un temps supérieur au temps nécessaire à l'équilibre de la réaction d'isomérisation sans destruction des sucres (c'est-à-dire à la durée de réaction permettant d'obtenir une sélectivité de 100 %), on vidange le réacteur, on stoppe la réaction par refroidissement brutal, on filtre la solution et on lave successivement le solide à la même température. On analyse ensuite les teneurs en glucose et en fructose de la solution liquide de réaction et de la solution issue de la désorption de la zéolithe.After a reaction time of 45 min, corresponding to a time greater than the time necessary to equilibrium of the isomerization reaction without destruction sugars (i.e. the reaction time allowing to obtain a selectivity of 100%), the reactor, the reaction is stopped by brutal cooling, the solution is filtered and the solid is successively washed at the same temperature. We then analyze the contents glucose and fructose from the liquid reaction solution and the solution resulting from the desorption of the zeolite.
Avec une quantité d'eau totale initiale de 230 g, la solution de glucose de départ avait une concentration de 500 g par litre.With an initial total water quantity of 230 g, the starting glucose solution had a concentration of 500 g per liter.
A la fin de la réaction (45 min), on retrouve les 170 g de sucre avec les proportions pondérales suivantes : 19 % de fructose, 80 % de glucose, et 1 % de mannose.At the end of the reaction (45 min), we find the 170 g of sugar with the weight proportions following: 19% fructose, 80% glucose, and 1% mannose.
On réalise le même essai que dans l'exemple 1 mais en plaçant le réacteur à 60° C.We carry out the same test as in the example 1 but placing the reactor at 60 ° C.
On retrouve, à l'issue de l'essai, 95 % des 170 g de sucre avec les proportions pondérales suivantes : 2 % de fructose, 98 % de glucose et 0 % de mannose.At the end of the test, 95% of the 170 g of sugar with the following weight proportions: 2% fructose, 98% glucose and 0% mannose.
Ces exemples démontrent que la zéolithe XK utilisée procure une adsorption sélective du glucose à 60° C sans isomérisation, et une excellente isomérisation du glucose en fructose à 95° C.These examples demonstrate that the XK zeolite used provides selective adsorption of glucose to 60 ° C without isomerization, and excellent isomerization glucose to fructose at 95 ° C.
Avec une telle zéolithe, on peut donc obtenir à la sortie 4 de l'installation représentée sur la figure, une solution pure de fructose, en continu, en une seule étape, et à un coût extrêmement faible.With such a zeolite, we can therefore get at exit 4 of the installation shown on the figure, a pure solution of fructose, continuously, in one single step, and at an extremely low cost.
Claims (15)
- A process for the continuous preparation of a solution of ketose, particularly ketohexose, from an initial sugar solution comprising at least one aldose, in particular at least one aldohexose, characterized by the use of at least one vertical continuous multi-contact reactor (1), by the fact that the initial sugar solution is introduced continuously into the reactor (1), that at least one tectosilicate or a clay suitable to form a heterogeneous catalyst for the isomerization of the aldoses and the ketoses is continuously circulated in the reactor (1), and that at least one microporous selective adsorption solid selected for the selective adsorption either of the aldoses from the initial solution or of the ketoses coming from the isomerization, while being compatible with the isomerization conditions, is circulated in downward direction in the reactor (1).
- A process according to Claim 1, characterized by the fact that:a single multi-contact reactor (1) is used;the initial sugar solution is introduced at an intermediate level of the reactor (1);at least one microporous solid of selective adsorption of the aldoses from the initial sugar solution is selected;a continuous stream of the solvent of the initial sugar solution is introduced into the reactor (1) at a level of the reactor below that at which the initial sugar solution is introduced;the solution of ketose is continuously extracted countercurrent at a level of the reactor (1) located above the level at which the initial sugar solution is introduced, so that the process can be carried out in single step in a single reactor (1).
- A process according to one of Claims 1 and 2, characterized by the fact that the temperature within the reactor or reactors (1) is controlled in at least two different zones (14, 15), the first of which (14) is maintained at a temperature of between 30°C and 90°C, selected so as to favor the adsorption by the microporous solid and the second of which (15) is maintained at a temperature of between 90°C and 110°C, selected so as to favor the isomerization of the aldoses into ketoses.
- A process according to Claim 3, characterized by the fact that a temperature of about 60°C is maintained in the first adsorption zone (14) and a temperature of about 95°C to 100°C is maintained in the second isomerization zone (15).
- A process according to one of Claims 3 and 4, characterized by the fact that the first adsorption zone (14) is located above the introduction (6) of the initial sugar solution into the reactor (1), and that the second isomerization zone (15) is located below the introduction (6) of the initial sugar solution into the reactor (1).
- A process according to one of Claims 1 to 5, characterized by the fact that as heterogenous isomerization catalyst there is used a tectosilicate or a clay in non-protonic form, functionalized by metal cations, in particular alkaline or alkaline-earth cations.
- A process according to one of Claims 1 to 6, characterized by the fact that a tectosilicate or a clay is used as microporous selective adsorption solid.
- A process according to one of Claims 1 to 7, characterized by the fact that a selective adsorption microporous solid in preformed pieces, in particular in extruded form, is used.
- A process according to one of Claims 1 to 8, characterized by the fact that a catalyst other than the selective microporous adsorption solid is used.
- A process according to one of Claims 1 to 8, characterized by the fact that a tectosilicate or a clay serving as isomerization catalyst and as microporous selective adsorption solid is used.
- A process according to Claim 10, characterized by the fact that the tectosilicate or clay is selected so that it serves as catalyst in a temperature range different from that in which it serves as selective microporous adsorption solid for the aldoses.
- A process according to one of Claims 10 and 11, characterized by the fact that an X zeolite in potassium or barium form is used.
- A process according to one of Claims 1 to 12, characterized by the fact that a pulsed column is used as reactor.
- An installation for the carrying out of the process according to one of Claims 1 to 13, characterized by the fact that it comprises a multi-contact vertical continuous reactor (1), in particular a pulsed column, and means (12, 13) for controlling the temperature prevailing within the reactor (1) in at least two different zones (14, 15) corresponding to at least two different temperatures.
- An installation according to Claim 13, characterized by the fact that it comprises an initial solution feed (6) located at an intermediate level of the reactor (1), and that the control means (12, 13) are adapted to control independently the temperature above and below the initial solution feed (6).
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR9414960A FR2727968A1 (en) | 1994-12-07 | 1994-12-07 | PROCESS FOR THE CONTINUOUS PREPARATION OF A CETOSE SOLUTION BY ISOMERIZATION OF ALDOSE, AND INSTALLATION FOR IMPLEMENTING SAME |
FR9414960 | 1994-12-07 | ||
PCT/FR1995/001616 WO1996017858A1 (en) | 1994-12-07 | 1995-12-06 | Method for continuously preparing a ketose solution by isomerising aldose, and apparatus therefor |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0796268A1 EP0796268A1 (en) | 1997-09-24 |
EP0796268B1 true EP0796268B1 (en) | 2000-03-29 |
Family
ID=9469737
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP95941781A Expired - Lifetime EP0796268B1 (en) | 1994-12-07 | 1995-12-06 | Method for continuously preparing a ketose solution by isomerising aldose, and apparatus therefor |
Country Status (8)
Country | Link |
---|---|
EP (1) | EP0796268B1 (en) |
AT (1) | ATE191220T1 (en) |
AU (1) | AU4308896A (en) |
BR (1) | BR9509901A (en) |
CA (1) | CA2207067A1 (en) |
DE (1) | DE69516017D1 (en) |
FR (1) | FR2727968A1 (en) |
WO (1) | WO1996017858A1 (en) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR101848794B1 (en) | 2010-01-15 | 2018-05-28 | 캘리포니아 인스티튜트 오브 테크놀로지 | Isomerization of sugars |
Family Cites Families (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US33105A (en) * | 1861-08-20 | Canteen-filler | ||
JPS5195143A (en) * | 1975-02-14 | 1976-08-20 | Gurukoosuno iseikahoho | |
JPS51110048A (en) * | 1975-02-21 | 1976-09-29 | Toray Industries | Toruino bunrihoho |
US4373025A (en) * | 1976-05-27 | 1983-02-08 | Uop Inc. | Process for the isomerization of glucose |
USRE33105E (en) * | 1982-12-30 | 1989-10-31 | Uop | Separation of mannose by selective adsorption on zeolitic molecular sieves |
FR2670209B1 (en) * | 1990-12-07 | 1995-04-28 | Commissariat Energie Atomique | PROCESS FOR THE PREPARATION OF FURFURAL HYDROXYMETHYL-5 BY HETEROGENEOUS CATALYSIS. |
-
1994
- 1994-12-07 FR FR9414960A patent/FR2727968A1/en active Pending
-
1995
- 1995-12-06 WO PCT/FR1995/001616 patent/WO1996017858A1/en active IP Right Grant
- 1995-12-06 BR BR9509901A patent/BR9509901A/en unknown
- 1995-12-06 CA CA002207067A patent/CA2207067A1/en not_active Abandoned
- 1995-12-06 AT AT95941781T patent/ATE191220T1/en not_active IP Right Cessation
- 1995-12-06 DE DE69516017T patent/DE69516017D1/en not_active Expired - Lifetime
- 1995-12-06 AU AU43088/96A patent/AU4308896A/en not_active Abandoned
- 1995-12-06 EP EP95941781A patent/EP0796268B1/en not_active Expired - Lifetime
Also Published As
Publication number | Publication date |
---|---|
CA2207067A1 (en) | 1996-06-13 |
ATE191220T1 (en) | 2000-04-15 |
BR9509901A (en) | 1997-09-16 |
MX9704207A (en) | 1997-09-30 |
WO1996017858A1 (en) | 1996-06-13 |
AU4308896A (en) | 1996-06-26 |
EP0796268A1 (en) | 1997-09-24 |
DE69516017D1 (en) | 2000-05-04 |
FR2727968A1 (en) | 1996-06-14 |
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